U.S. patent number 4,276,414 [Application Number 06/189,397] was granted by the patent office on 1981-06-30 for novel zwitterion polygalactomannan ether derivatives and a method for the preparation thereof.
This patent grant is currently assigned to National Starch and Chemical Corporation. Invention is credited to Martin M. Tessler.
United States Patent |
4,276,414 |
Tessler |
June 30, 1981 |
Novel zwitterion polygalactomannan ether derivatives and a method
for the preparation thereof
Abstract
Zwitterion polygalactomannan ether derivatives are prepared by
reacting a polygalactomannan gum, such as guar gum or locust bean
gum, with N-(2-haloethyl)iminobis(methylene)diphosphonic acid or
with a N-(alkyl)-N-(2-haloethyl)aminomethylphosphonic acid. The
derivatives contain aminophosphonic acid groups (or their salts) as
zwitterion substituents which consist of either one or two anionic
methylene phosphonic acid groups bound to a cationic nitrogen.
Modified derivatives containing non-ionic, anionic, cationic, or
cationogenic substituents may also be prepared.
Inventors: |
Tessler; Martin M. (Edison,
NJ) |
Assignee: |
National Starch and Chemical
Corporation (Bridgewater, NJ)
|
Family
ID: |
26804687 |
Appl.
No.: |
06/189,397 |
Filed: |
September 22, 1980 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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107347 |
Dec 26, 1979 |
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Current U.S.
Class: |
536/114; 536/120;
536/122 |
Current CPC
Class: |
C08L
5/00 (20130101) |
Current International
Class: |
C08B
37/00 (20060101); C08B 37/14 (20060101); C08B
037/00 (); C07G 017/00 () |
Field of
Search: |
;536/114,117,116,120,52 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Brown; Johnnie R.
Assistant Examiner: Hazel; Blondel
Attorney, Agent or Firm: Szala; Edwin M. Kelley; Margaret
B.
Parent Case Text
This application is a continuation-in-part of my copending
application, Ser. No. 107,347, filed Dec. 26, 1979, now abandoned.
Claims
What is claimed is:
1. As a composition of matter, a zwitterion polygalactomannan ether
derivative of the general structure ##STR4## or a combination of
(i) and (ii), wherein Gum-O represents a polygalactomannan gum
molecule; R is a C.sub.1 -C.sub.6 alkyl group, a C.sub.3 -C.sub.6
cycloalkyl group or a ##STR5## M is a cation; and n is the valence
number of M.
2. The zwitterion derivative of claim 1, wherein M is hydrogen, an
alkali, or an alkaline earth metal and said polygalactomannan is a
guar gum or a locust bean gum.
3. The zwitterion derivative of claim 1, wherein R is an ethyl,
n-butyl, or cyclohexyl group and M is sodium.
4. The zwitterion derivative of claim 1, wherein said
polygalactomannan gum molecule contains non-ionic, anionic,
cationic, or cationogenic groups and said polygalactomannan is a
guar gum or a locust bean gum.
5. A derivative of claim 4, wherein said non-ionic groups are
2-hydroxypropyl ether groups, said anionic groups are carboxymethyl
groups, and said cationic or catinogenic groups are
3-(trimethylammonium chloride)-2-hydroxypropyl ether groups or
diethyl aminoethyl ether groups.
6. The zwitterion derivative of claim 5, wherein R is an ethyl,
n-butyl, or cyclohexyl group and M is sodium.
7. A method for preparing a zwitterion polygalactomman ether
derivative of the general structure ##STR6## or a combination of
(i) and (ii), wherein Gum-O represents a polygalactomanan gum
molecule; R is a C.sub.1 -C.sub.6 alkyl group, a C.sub.3 -C.sub.6
cycloalkyl group or a ##EQU1## M is a cation; and n is the valence
number of M, which comprises the steps of:
a. reacting a polygalactomannan gum base with about 0.1 to 100% by
weight, based on the dry gum, of a zwitterion reagent having the
general formula ##EQU2## wherein X is chlorine or bromine, R is a
C.sub.1 -C.sub.6 alkyl group, a C.sub.3 -C.sub.6 cycloalkyl group,
or a ##EQU3## M is a cation, and n is the valence number of M; and
b. isolating the resulting zwitterion polygalactomannan ether
derivative.
8. The method of claim 7, wherein said reaction is carried out in
an aqueous medium containing a water-miscible solvent and 0.05-20%
excess alkali, based on the dry gum, at a temperature of
15.degree.-100.degree. C. for 0.5-8 hours.
9. The method of claim 7, wherein said reaction is carried out in
aqueous isopropanol at a temperature of 20.degree.-60.degree. C.
for 1-5 hours.
10. The method of claim 7, wherein said polygalactomannan gum is a
guar gum or a locust bean gum, optionally containing non-ionic,
anionic, cationic, or cationogenic groups.
11. The method of claim 10, wherein said gum contains
2-hydroxypropyl ethyl groups, carboxy methyl groups,
3-(trimethylammonium chloride)-2-hydroxypropyl ether groups, or
diethyl aminoethyl ether groups.
12. The method of claim 7, wherein said zwitterion reagent is
selected from the group consisting of
N-(2-chloroethyl)iminobis(methylene)diphosphonic acid,
N-(2-bromethyl)iminobis(methylene)diphosphonic acid,
N-(ethyl)-N-(2-chloroethyl)aminomethylphosphonic acid,
N-(n-butyl)-N-(2-chloroethyl)aminomethylphosphonic acid, and
N-(cyclohexyl)-N-(2-chloroethyl)aminomethylphosphonic acid.
Description
BACKGROUND OF THE INVENTION
This invention relates to novel zwitterion polygalactomannan ether
derivatives and to a method for their preparation. It also relates
to modified polygalactomannan ether derivatives which contain, in
addition to the novel zwitterion substituent groups, other
non-ionic, anionic, cationic, or cationogenic substituent groups
and to a method for their preparation.
As used herein, the term "zwitterion polygalactomannan ether
derivatives" includes amphoteric polygalactomannan ether
derivatives wherein the anionic and cationic or cationogenic
substituent groups are both bonded to the same reaction site on the
polygalactomannan molecule through a zwitterion substituent group.
The term "cationogenic" refers to non-ionic substituents capable of
forming cations, e.g. diethylaminoethyl ether substituents.
Polygalactomannan ether derivatives are well-known in the art and
useful in the petroleum industry as oil well drilling muds and oil
well fracturing aids, in the textile industry for sizing, printing
and finishing operations, and in the paper industry as beater
additives and sizing and coating agents. Typical derivatives may
contain non-ionic groups, such as C.sub.3 -C.sub.8 -hydroxyalkyl
groups or allyl groups, anionic groups, such as carboxyalkyl groups
or 2-hydroxy-3-sulfopropyl groups; cationic groups, such as
quaternary or tertiary amine groups; and mixed ether groups, such
as carboxyalkyl and hydroxyalkyl groups.
It is an object of this invention to provide novel zwitterion
polygalactomannan ether derivatives and modified zwitterion
polygalactomannan ether derivatives which will be useful in the
paper industry as beater additivers, sizing and coating agents, and
pigment retention aids, as in well as the textile and petroleum
industries.
SUMMARY OF THE INVENTION
The above object is achieved by the preparation of novel zwitterion
polygalactomannan ether derivatives of the general structures (i)
or (ii) or a combination of (i) and (ii), ##STR1## wherein Gum-O
represents a polygalactomannan molecule or a modified
polygalactomannan molecule (wherein the hydrogen of a hydroxyl
group of a mannose or galactose unit has been replaced as shown); R
is a C.sub.1 -C.sub.6 straight or branched chain alkyl group, a
C.sub.3 -C.sub.6 cycloaklyl group, or a ##STR2## M is the same or
different cation(s); and n is the valence number of M. The
zwitterion polygalactomannan ether derivatives are prepared by
reacting polygalatomannan gum with about 0.1 to 100% by weight,
based on dry gum, of N-(2-haloethyl)iminobis(methylene)diphosphonic
acid or with about 0.1 to 100% by weight, based on dry gum, of a
N-alkyl-N-(2-haloethyl)-aminomethylphosphonic acid and isolating
the resulting gum derivatives. The reactions are carried out under
alkaline conditions in an aqueous solution containing a
water-miscible solvent.
The zwitterion gum ether derivatives may be modified to increase
their cationic or anionic characteristics. When increased anionic
properties are desired, anionic substituent groups, such as
carboxymethyl groups, are introduced into the gum molecule using
suitable reagents. When increased cationic properties are desired,
cationic or cationogenic substituent groups, such as
3-(trimethylammonium chloride)-2-hydroxypropyl ether groups or
diethyl aminoethyl ether groups, are introduced into the gum
molecule using suitable reagents. The zwitterion gum ether
derivatives may also be modified by the introduction of non-ionic
substituent groups such as 2-hydroxypropyl ether groups. Reaction
with the non-ionic, anionic, cationic, or cationogenic reagent may
be carried out prior to or after reaction with the aminophosphonic
acid (or salt) reagent or the two reactions may be carried out
simultaneously.
The zwitterion gum ether derivatives and modified zwitterion gum
ether derivatives may be used as wet end additives and in many
other applications wherein gum ether derivatives are commonly used.
They are particularly useful as pigment retention aids in
papermaking processes.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The "polygalactomannan gums" suitable for reaction herein are
heteropolysaccharides composed principally of long chains of
mannose units and single unit side chains of galactose units. They
are commonly found in the endosperm of certain seeds of the plant
family "Leguminosae", such as the seeds of guar, locust bean, honey
locust, flame tree, and the like. They may be used in the form of
endosperm "splits", i.e. tough, non-brittle endosperm sections (see
U.S. Pat. No. 3,132,681 for a method for separating the splits) or
preferably in the form of purified or unpurified ground endosperm
(see U.S. Pat. Nos. 2,891,050 and 3,455,899). Also suitable for use
herein are gum degradation products resulting from the hydrolytic
action of acid, heat, shear, and/or enzymes; oxidized gums;
derivatized gums such as esters or ethers; and other typical
carbohydrate modifications.
The preferred gums are guar gum and locust bean gum because of
their commercial availability. Guar gum is essentially a straight
chain mannan wherein the mannose units are linked in a
1,4-.beta.-glycosidic linkage and the galactose branching takes
place by means of a 1,6 linkage on alternate mannose units
(galactose to mannose ratio of 1:2). If desired, guar gum may be
purified according to the method described in U.S. Pat. No.
4,031,306, in which case the residual nitrogen content will
decrease from about 0.7% to less than 0.1%. Locust bean gum has a
structure similar to guar gum, wherein the galactose to mannose
ratio is 1:4, but wherein the branching is not uniformly
spaced.
The N-(2-haloethyl)iminobis(methylene)diphosphonic acid reagent,
which reacts with the gum to form zwitterion polygalactomannan
ether derivatives containing amino-diphosphonic acid groups (or
salt groups), may itself be prepared by reacting a 2-haloethylamine
with formaldehyde and phosphorous acid in an aqueous hydrohalic
acid. The method is analogous to that disclosed by K. Moedritzer
and R. Irani in J. Org. Chem. 31, 1603 (1966). Specifically
phosphorous acid, in a stoichiometric amount or in an excess of up
to 100%, is dissolved in water and a 2-haloethylamine hydrochloride
is added. Aqueous hydrohalic acid is slowly added and the mixture
is heated to reflux. Formaldehyde (10-200% excess) is added, and
the solution is refluxed for 1-20 hours, preferably 2-6 hours,
cooled to room temperature, and stripped of excess water,
formaldehyde and hydrohalic acid. The product sometimes
crystallizes as a very hard mass. It is preferable to add water and
alkali to the acid product to form a 20-50% aqueous solution having
a pH of 1.5-2.7. The halo groups for use herein are chloro and
bromo. The preferred reagents are 2-chloroethylamine hydrochloride
and 2-bromoethylamine hydrobromide. The preferred hydrohalic acid
is hydrochloric acid.
The N-(alkyl)-N-(2-haloethyl)aminomethylphosphonic acids, which
react with the gum to form zwitterion polygalactomannan ether
derivatives containing amino-monophosphonic acid groups (or salt
groups), may be prepared by a variation of the procedure described
above, except that a N-(2-haloethyl)alkylamine hydrochloride or
hydrobromide is used as the starting material. The halo groups for
use herein are chloro and bromo. Examples of suitable
N-(alkyl)-N-(2-haloethyl)aminomethylphosphonic acids include the
N-(methyl)-, N-(ethyl)-, N-(propyl)-, N-(butyl)-, and
N-(cyclohexyl)-N-(2-haloethyl)aminomethylphosphonic acids. The
alkyl groups may be linear, branched or cyclic. The preferred
reagents for use herein include N-(ethyl)-, N-(n-butyl)- and
N-(cyclohexyl)-N-(2-chloroethyl)aminomethylphosphonic acids.
The N-(2-haloethyl)alkylamine hydrochlorides, which are used in the
preparation of the amino-monophosphonic acid reagents, are
themselves prepared by reacting a 2-(alkylamino)ethanol with
thionyl chloride in an organic solvent. Specifically, a
2-alkylamino)ethanol is added to toluene and the solution is cooled
to -10.degree. C. A solution of thionyl chloride in an organic
solvent (e.g. toluene) is slowly added while maintaining the
temperature at below -10.degree. C. Additional toluene may be added
and the temperature is increased to abut 75.degree.-100.degree. C.
The solution is agitated for 1 hour, cooled and then maintained at
75.degree.-82.degree. C. for 3 hours. After cooling to room
temperature, the insoluble product is recovered by filtration. The
preferred reagents for use herein include 2-(ethylamino)ethanol,
2-(n-butylamino)ethanol, and 2-(cyclohexylamino)-ethanol.
These reagents will be referred to herein as zwitterion reagents
and this term is meant to include both the
N-(2-haloethyl)iminobis(methylene)disphosphonic acids and the
N-(alkyl)-N-(2-haloethyl)aminomethylphosphonic acids. The
practitioner will recognize that these zwitterion reagents are
acids or partially neutralized acids under the conditions used for
their preparation and storage but are acid salts under the alkaline
conditions used for their reactions with the gum.
The practitioner will recognize that the reaction conditions used
in the above reagent preparations may have to be altered depending
on the nature of the starting materials and that it may be possible
to prepare the reagents by other methods.
The polygalactomannan reactions of this invention are represented
by the equations below: ##STR3## wherein Gum is a polygalactomannan
gum base or a modified gum base such as non-ionic, anionic,
cationic, or cationogenic gums; X is a halogen, preferably chlorine
or bromine; R.sub.1 is a C.sub.1 -C.sub.6 straight or branched
chain alkyl group or a C.sub.3 -C.sub.6 cycloalkyl group; and M is
one or more cations depending on the valence of M, preferably
selected from the group consisting of hydrogen, ammonium, alkali,
and alkaline earth metals. The practitioner will recognize that at
the high pH of the gum reactions the nitrogen may not be
protonated; however the nitrogen will become protonated if the
excess alkali is neutralized before isolating the derivative.
The polygalactomannan ether derivatives prepared by the above
reactions are referred to herein as zwitterion polygalactomannan
ether derivatives, and this term is meant to include those
derivatives which contain the amino-diphosphonic acid (or salt) as
well as those which contain the amino-monophosphonic acids (or
salts). The practitioner will recognize that these derivatives may
be either acids, salts, or partial salts depending upon the pH of
the solution wherein they are used.
The practitioner will also recognize that the gum molecule is a
polymer which contains many anhydro sugar units, each having on the
average three available hydroxyl sites which may react with
reagent. Thus, the number of such displacements or the degree of
substitution (D.S.) will vary with the particular gum, the ratio of
reagent to gum, and, to some extent, the reaction conditions.
Furthermore, since it is known that the relative reactivity of each
of the hydroxyl groups within the anhydro sugar unit is not
equivalent, it is probable that some will be more reactive with the
reagent than others.
In the method of this invention, the reaction is carried out in a
two-phase reaction system comprising an aqueous solution of a
water-miscible solvent and water-soluble zwitterion reagent in
contact with the solid polygalactomannan gum. The water content may
vary from 10-60% by weight depending upon the water-miscible
solvent selected. If too much water is present in the reaction
system, the gum may swell or enter into solution thereby
complicating recovery and purification of the gum derivative.
The water-miscible solvent is added in an amount sufficient for the
preparation of a gum suspension which can be agitated and pumped.
The weight ratio of water-miscible solvent to gum may vary from 1:1
to 10:1, preferably from 1.5:1 to 5:1.
Suitable water-miscible solvents for use herein include alkanols,
glycols, cyclic and acylic alkyl ethers, alkanones,
dialkylformamide and mixtures thereof. Typical solvents include
methanol, ethanol, isopropanol, secondary pentanol, ethylene
glycol, acetone, methylethylketone, diethylketone, tetrahydrofuran,
dioxane, and dimethylformamide.
The amount of zwitterion reagent to be employed in the reaction
with the gum herein will vary from about 0.1 to 100% by weight,
based on the weight of dry gum, depending on such factors as the
gum used, the zwitterion reagent used, the degree of substitution
required in the end product, and, to some extent, the reaction
conditions used. In general, the preferred amount of reagent to be
used when preparing the zwitterion polygalactomannan ether
derivatives containing amino-diphosphonic acid groups or
amino-monophosphonic groups (or salt groups) is 1-30% by
weight.
The zwitterion reagent may be added to the reaction mixture as a
solid or an aqueous solution. The preferred concentration of the
solution is 20-50% by weight, based on weight of reagent. In an
alternative method, the zwitterion reagent solution is brought to
the desired alkaline pH prior to its addition to the gum, this
being accomplished by the addition of sufficient alkali. In this
alternative method, the zwitterion reagent is in the form of a salt
rather than an acid or partially neutralized acid when it is
introduced to the reaction mixture. In another variation dry gum
may be added to an alkaline solution of the aminophosphonic acid
salt.
The gum reaction is carried out under alkaline conditions. Alkali
may be added to the gum suspension either prior to or after the
addition of the zwitterion acid reagent. Typical alkalies include
sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium
hydroxide, tetramethylammonium hydroxide, and the like. The
preferred alkali is sodium hydroxide. Some of the alkali functions
as a reactant, i.e. neutralizes the hydrochloric acid formed when
the gum reacts with the zwitterion reagent, and some of the alkali
functions as a catalyst. An excess of alkali is therefore required
to catalyze the reaction. The excess alkali which functions as the
catalyst can vary in amount from about 0.05 to 20% by weight, based
on the weight of gum. This excess alkali is not consumed during the
gum etherification reaction.
The reaction is carried out at a temperature of from
15.degree.-100.degree. C., preferably 20.degree.-60.degree. C. The
reaction mixture is agitated under the desired reaction conditions.
The reaction time may vary from 0.5 to 8 hours, depending on such
factors as the amount, stability and reactivity of the zwitterion
reagent employed, the temperature, the pH, the scale of the
reaction, and the degree of substitution desired. In general, the
preferred range of reaction times is from 1 to 5 hours.
After completion of the reaction, it is preferred that the excess
alkali be neutralized with an acid such as hydrochloric acid,
sulfuric acid, acetic acid, and the like.
After completion of the etherification reaction, the solid
polygalactomannan zwitterion ether derivatives are separated from
the reaction mixture by centrifugation or filtration. The solid
derivative so recovered is preferably further treated and purified
by washing with the same aqueous solution of water-miscible solvent
as previously employed in the reaction and then by further washing
with a more anhydrous form of the same solvent.
Modified zwitterion gum ether derivatives may also be prepared
which contain, in addition to the novel zwitterion substituent
groups described herein, non-ionic, anionic, cationic, or
cationogenic groups. The preferred non-ionic groups are
2-hydroxypropyl groups (see U.S. Pat. No. 3,723,408 for the
preparation of such non-ionic derivatives). The preferred anionic
groups are carboxyalkyl groups (see U.S. Pat. Nos. 2,477,544 and
2,520,161 for the preparation of such anionic derivatives). The
preferred cationic groups are quaternary amine groups, such as
3-(trimethylammonium chloride)-2-hydroxypropyl groups or
4-(trimethylammonium chloride)-2-butenyl groups (see U.S. Pat. No.
4,031,307 for the preparation of the latter cationic derivatives);
the preferred cationogenic groups are tertiary amino groups, such
as diethyl aminoethyl ether groups.
There are three possible ways to prepare the modified zwitterion
gum ether derivatives: (1) a non-ionic, anionic, cationic, or
cationogenic gum derivative is reacted with a zwitterion reagent of
this invention; (2) a zwitterion gum ether derivative of this
invention is reacted with a non-ionic, anionic, cationic, or
cationogenic reagent(s); or (3) a gum base is reacted in one step
with both a zwitterion reagent of this invention and a non-ionic,
anionic, cationic, or cationogenic reagent(s).
The above reactions are carried out in the presence of excess
alkali using a method similar to that used for preparing the
unmodified zwitterion derivatives, i.e. a two phase reaction system
comprising an aqueous solution containing a water-miscible solvent
and a water-soluble reagent in contact with the solid gum. The
skilled practitioner will recognize that gum esters are not very
stable at high pH and, hence, zwitterion derivatives containing
ester substituents must be prepared by method (2) to avoid ester
hydrolysis under the alkaline conditions required to prepare the
gum zwitterion derivatives.
It can be appreciated by the practitioner that a large number of
variations may be effected in selecting the non-ionic, anionic,
cationic, and cationogenic reagents and in reacting the gum base
with the zwitterion reagents, the zwitterion and non-ionic
reagent(s), the zwitterion and anionic reagent(s), and the
zwitterion and cationic (or cationogenic) reagent(s) in accordance
with the reaction procedures described above without materially
departing from the scope and spirit of the invention. Such
variations will be evident to those skilled in the art and are to
be included within the scope of this invention.
The following examples will more fully illustrate the embodiments
of this invention. In the examples, all parts and percentages are
given by weight, all temperatures are in degrees Celsius unless
otherwise noted, and D.B. indicates dry basis. The nitrogen content
of any particular gum derivative may be determined by comparing the
amount of nitrogen contained in the derivative with that of a
control polygalactomannon gum which had been similarly treated in
the absence of zwitterion reagent. The nitrogen content was
determined by the Kjeldahl method.
EXAMPLE I
This example illustrates the preparation of zwitterion reagents for
use in the preparation of the novel zwitterion polygalactomannon
ether derivatives. The final solutions were used for the gum
reactions described herein.
A. Preparation of N-(2-Chloroethyl)iminobis(methylene)diphosphonic
Acid (Zwitterion Reagent A)
A total of 29 parts 2-chloroethylamine hydrochloride was added to
41.5 parts phosphorous acid in 50 parts water. Then 59 parts of 37%
aqueous hydrochloric acid were added slowly over the period of
about 0.5 hour, and the mixture was slowly brought to reflux over
the period of about 1 hour. While maintaining reflux at a constant
rate, 81 parts of 37% aqueous formaldehyde were added dropwise over
a period of about 0.75 hours. The mixture was refluxed for 3 hours,
cooled to 24.degree. C. and stripped of volatiles at 40.degree. C.
in a rotary evaporator (water aspirator) to yield a concentrate. An
equal amount of water (i.e. 84 parts) was added to the concentrate
and the pH was raised to 1.5 with 25% aqueous sodium hydroxide
while maintaining the temperature at below 35.degree. C.
B. Preparation of N-(2-Bromoethyl)iminobis(methylene)diphosphonic
Acid (Zwitterion Reagent B)
The procedure described in Preparation A was followed except that
51 parts 2-bromoethylamine hydrobromide, 100 parts of 48% aqueous
hydrobromic acid and 81 parts of 37% aqueous formaldehyde were
used. Then 109 parts water were added to the concentrate and the pH
was raised to 2.5.
C. Preparation of N-(Ethyl)-N-(2-chloroethyl)aminomethylphosphonic
Acid (Zwitterion Reagents C-1 and C-2)
The procedure described in Preparation A was followed except that
36 and 72 parts of N-(2-chloroethyl)ethylamine hydrochloride were
used to prepare C-1 and C-2, respectively. Then 75 parts water were
added and the pH adjusted to 1.5.
D. Preparation of
N-(n-Butyl)-N-(2-chloroethyl)aminomethylphosphonic Acid (Zwitterion
Reagents D-1 and D-2)
The procedure described in Preparation C was followed except that
43 and 86 parts of N-(2-chloroethyl)-n-butylamine hydrochloride
were used instead of N-(2-chloroethyl)ethylamine hydrochloride to
prepare D-1 and D-2, respectively.
E. Preparation of
N-(Cyclohexyl)-N-(2-chloroethyl)-aminomethylphosphonic Acid
(Zwitterion Reagents E-1 and E-2)
The procedure described in Preparation C was followed except that
40 parts of N-(2-chloroethyl)cyclohexylamine hydrochloride were
used instead of N-(2-chloroethyl)ethylamine hydrochloride to
prepare E-1.
A total of 101 parts of N-(2-chloroethyl)cyclohexylamine
hydrochloride, 41.5 parts phosphorous acid in 101 parts water, 75
parts of 37% aqueous hydrochloric acid, and 104 parts of 37%
aqueous formaldehyde were used to prepare E-2.
EXAMPLE II
This example illustrates the preparation of the zwitterion guar gum
ether derivatives.
Guar Gum A--Derivative Containing Amino-Diphosphonic Acid
Groups
A total of 30 parts of unpurified guar gum was added to 180 parts
of 50% aqueous isopropanol and the suspension was stirred for one
hour at 40.degree. C. under nitrogen. Then 3.6 parts of 50% aqueous
sodium hydroxide (1.8 parts D.B.) were added, and the mixture was
stirred for 10 minutes at 40.degree. C. Then 31.4 parts of a 23.9%
aqueous solution of Zwitterion Reagent A (7.5 parts D.B.) and 6.5
parts of 50% aqueous sodium hydroxide (3.25 parts D.B.) were added.
The reaction mixture was stirred at 40.degree. C. for 4 hours. The
pH was lowered to 8.3 with dilute acetic acid, and the guar gum
derivative was recovered by filtration, washed twice with 50%
aqueous isopropanol and once with isopropanol, and air dried. It
contained 1.10% N (D.B.).
Guar Gum B--Control Sample
A sample of guar gum was reacted in the same manner as above,
except that Zwitterion Reagent A was omitted. It contained 0.46% N
(D.B.). Thus, Guar A contained 0.64% N from the aminodiphosphonic
acid substituent.
Guar Gums C-1 and C-2--Derivatives Containing Amino-Monophosphonic
Acid and N-Ethyl Groups
A sample of guar gum was reacted in the same manner as above except
that 40.7 parts of a 18.4% aqueous solution of Zwitterion Reagent
C-1 (7.5 parts D.B.) were used and 6.6 parts of 50% aqueous sodium
hydroxide (3.3 parts D.B.) were subsequently added. The guar
derivative (C-1) contained 0.99% N (D.B.) of which 0.53% was from
the amino-monophosphonic acid substituent.
The same procedure was followed except that 10.5 parts of a 43.0%
aqueous solution of Zwitterion Reagent C-2 (4.5 parts D.B.) and 7.6
parts of 50% aqueous sodium hydroxide (3.8 parts D.B.) were used.
The guar derivative (C-2) contained 1.0% N (D.B.) of which 0.54%
was from the amino-monophosphonic acid substituent.
Guar Gum D--Derivative Containing Amino-Monophosphonic Acid and
n-Butyl Groups
A sample of guar gum was reacted in the same manner as above except
that 15.4 parts of a 29.3% aqueous solution of Zwitterion Reageant
D-2 (4.5 parts D.B.) and 7.6 parts of 50%, aqueous sodium hydroxide
(3.8 parts D.B.) were used. The guar derivative contained 1.0% N
(D.B.) of which 0.54% was from the amino-monophosphonic acid
substituent.
Guar Gum E--Derivative Containing Amino-Monophosphonic Acid and
Cyclohexyl Groups
A sample of guar gum was reacted in the same manner as above except
that 22.7 parts of a 19.9% aqueous solution of Zwitterion Reagent
E-2 (4.5 parts D.B.) and 7.8 parts of 50 aqueous sodium hydroxide
(3.9 parts D.B.) were used. The guar derivatives contained 0.76% N
(D.B.).
EXAMPLE III
This example illustrates the preparation of the zwitterion locust
bean gum derivative.
Locust Bean Gum A--Derivative Containing Amino-Diphosphonic Acid
Groups
The procedure described in Example II for Guar Gum A was followed
except guar gum was replaced by locust bean gum and 38.1 parts of
19.7% aqueous solution of Zwitterion Reagent A (7.5 parts D.B.) and
4.0 parts of 50% aqueous sodium hydroxide (2.0 parts D.B.) were
used. The locust bean derivative contained 1.50% N(D.B.) of which
0.57% was from the aminodiphosphonic acid substituent. The control
locust bean gum, reacted in the same manner except that Zwitterion
Reagent A was omitted, contained 0.93% N(D.B.).
EXAMPLE IV
This example describes the preparation of another guar gum
derivative.
Guar Gum F--Derivative Containing Amino-Diphosphonic Acid
Groups
A sample of guar gum is reacted in the same manner as in Example II
except that 25.5 parts of a 23.5% aqueous solution of Zwitterion
Reagent B (6.0 parts D.B.) are used.
EXAMPLE V
This example illustrates the use of the zwitterion guar gum ether
derivatives as pigment retention aids in the manufacture of
paper.
Guar Gum A (derivative containing amino-diphosphonic acid groups)
and Guar Gum C-1 (derivative containing amino-monophosphonic acid
groups) were each added at a concentration of 0.25%, based on the
weight of the dry pulp, to three bleached sulfite pulps which
contained a varied amount of paper alum, i.e. aluminum sulfate. The
three pulps contained 0%, 4.0%, and 11.0% alum, by weight based on
the dry pulp. In each case, the pigment retention value of the test
paper stock and those of the control and comparative sample were
determined by first preparing paper sheets on the Williams Standard
Sheet mold and then testing for the percent of titanium dioxide
(TiO.sub.2) retained by the method described in TAPPI Standard
#T413 m. 58. The control consisted of unreacted guar gum. The
comparative sample consisted of an amphoteric starch ether
derivative of the prior art, i.e., the phosphorylated,
diethylaminoethyl ether of corn starch, containing 0.32% nitrogen
and 0.08% phosphorous by weight, prepared as described in U.S. Pat.
No. 3,459,632.
The results are summarized in Table I. The data indicate that both
guar gum derivatives are superior to the amphoteric starch
derivative.
TABLE I ______________________________________ %TiO.sub.2 Retention
in the presence of the following amounts of alum Material Tested 0%
4.0% 11.0% ______________________________________ Guar Gum
(control) 65.9 54.2 54.6 Amphoteric Starch Ether 53.8 60.8 54.8
(comparative) Guar Gum A 66.5 66.1 72.4 Guar Gum C-1 65.4 69.4 67.0
______________________________________
EXAMPLE VI
This example describes the preparation of modified zwitterion guar
gum ether derivatives.
Part A - Derivatives Containing Cationic and Cationogenic Groups
Guar Gum G--Derivative Containing Amino-Diphosphonic Acid Groups
and Tertiary Amine Groups
A cationic guar gum derivative containing diethyl aminoethyl ether
groups is prepared by adding 30 parts of unpurified guar gum to 180
parts of 50% aqueous isopropanol, stirring the suspension for one
hr at 40.degree. C. under nitrogen, adding 3.6 parts of 50% aqueous
sodium hydroxide, and stirring for 10 mins at 40.degree. C. Then
2.4 parts of 50% aqueous 2-diethylaminoethylchloride hydrochloride
are added, the mixture is stirred for 5 hrs at 40.degree. C. The pH
is then lowered to 8.0 with dilute acetic acid, and the derivative
is recovered by filtration washed with 50% aqueous isopropanol and
then with 100% isopropanol, and air dried.
The cationic guar gum derivative is then reacted with Zwitterion
Reagent A using the same procedure and amounts used for the
preparation of Guar Gum A of Example II. Guar Gum H--Derivative
Containing Amino-Diphosphonic Acid Groups and Quaternary Ammonium
Groups.
A cationic guar gum derivative containing 3-(trimethylammonium
chloride-2-hydroxypropyl groups is prepared in the same manner as
above except that 2.4 parts of 50% aqueous 3-chloro-2-hydroxypropyl
trimethylammonium chloride are used instead of
2-diethylaminoethylchloride hydrochloride.
The cationic derivative is then reacted with Zwitterion Reagent A
using the same procedure and amounts used for the preparation of
Guar Gum A of Example II.
Part B - Derivative Containing Anionic Groups
Guar Gum I--Derivative Containing Amino-Diphosphonic Acid Groups
and Carboxyalkyl Groups.
An anionic guar gum derivative containing carboxymethyl groups is
prepared in the same manner as the cationic guar gum derivative
described in the preparation of Guar Gum G except that the reaction
temperature should be increased to 60.degree. C. and 2.0 parts
sodium chloroacetate are used instead of
2-diethylaminoethylchloride hydrochloride.
The anionic derivative is then reacted with Zwitterion Reagent A
using the same procedure and amounts used for the preparation of
Guar Gum A of Example II.
Part C - Derivative Containing Non-Ionic Groups
Guar Gum J--Derivative Containing Amino-Diphosphonic Acid Groups
and 2-Hydroxypropyl Groups.
An non-ionic guar gum derivative containing 2-hydroxypropyl groups
is prepared in the same manner as the anionic guar gum derivative
described in the preparation of Guar Gum I except that 70% aqueous
isopropanol is used instead of 50% aqueous isopropanol, 3.0 parts
propylene oxide are used instead of sodium chloroacetate, and 1.8
parts of 50% aqueous sodium hydroxide are used instead of 3.6 parts
of aqueous sodium hydroxide.
The non-ionic derivative is then reacted with Zwitterion Reagent A
using the same procedure and amounts used for the preparation of
Guar Gum A of Example I.
Summarizing, this invention is seen to provide novel zwitterion
polygalactomannan ether derivatives containing amino-diphosphonic
acid groups or amino-monophosphonic acid groups (or their salts)
and modified zwitterion polygalactomannan derivatives containing
non-ionic, anionic, cationic, or cationogenic groups.
Now that the preferred embodiments of the present invention have
been described in detail, various modifications and improvements
thereon will become readily apparent to those skilled in the art.
Accordingly, the spirit and scope of the invention are to be
limited only by the appended claims and not by the foregoing
specifications.
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